CN107369833A - A kind of preparation method of network-like carbon negative pole material - Google Patents
A kind of preparation method of network-like carbon negative pole material Download PDFInfo
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- CN107369833A CN107369833A CN201710529304.0A CN201710529304A CN107369833A CN 107369833 A CN107369833 A CN 107369833A CN 201710529304 A CN201710529304 A CN 201710529304A CN 107369833 A CN107369833 A CN 107369833A
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- negative pole
- pole material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of preparation method of network-like carbon negative pole material.The present invention, as electrolyte, network-like carbon negative pole material is obtained by post processings such as electrolysis using alcoholic solvent and alkali.Network-like carbon negative pole material has open, porous, interworking architecture, overcomes flaky material agglomeration, is had a good application prospect in lithium ion and sodium-ion battery equal energy source field of storage.
Description
Technical field
The present invention relates to a kind of method that network-like carbon negative pole material is prepared using electrolysis tech, and in particular to one kind uses
The method that alcoholic solvent and highly basic synthesize network-like carbon negative pole material, belong to carbon functional material synthesis field.
Background technology
At present, Two-dimensional Carbon material preparation method mainly include mechanical stripping method, chemistry redox technology, high temperature cabonization with
And chemical vapour deposition technique.Wherein, mechanical stripping and chemical vapour deposition technique, yield is extremely low, is not suitable for prepare with scale；
Although graphite oxidation reduction technique can be to use strong acid, strong oxidizer and reducing agent in magnanimity preparation process, process is cumbersome, pollution
It is larger；Using metal such as copper foil etc. as catalysts template chemical vapor deposition preparation process harshness need to shift use, low yield,
Be not suitable for magnanimity production；Use metal oxide to prepare two-dimentional carbon material for template to make, it is necessary to react by sequence of chemical in advance
It is standby to obtain nano-oxide, then Two-dimensional Carbon materials synthesis is carried out, equally using other templates such as diatomite etc., not only need to mould
The pre-etching of plate strong acid is handled, and also needs to remove removing template using the strong hydrofluoric acid of corrosivity or highly basic after high―temperature nuclei；Using biomass
Hard carbon material obtained by carbonization technology is, it is necessary to very high temperature（Higher than 1000 DEG C）, presoma source is difficult to ensure card, quality by region and
Climate influences big.Can obtaining the graphene network structure with three-dimensional structure using solid-phase sintering technology, [a kind of solid is nitrogenous
Organic acid synthesizes the method for azepine graphene, number of patent application：201510333237.6；One kind is by metal salts of organic acids compound stone
The method of black alkene, number of patent application：201310296522.6]；It can also be made using carbon quantum dot self assembly combination sintering method
It is standby go out three-dimensional carbon network structure [HS Hou, CE. Banks, MJ Jing, Y Zhang, XB Ji, Carbon quantum dots
and their derivative 3D porous carbon frameworks for sodium-ion batteries
With ultralong cycle life, Adv. Mater. 2015,27,7861-7866].And above-mentioned network-like carbon nanometer material
Material has open, porous, interworking network structure, and this network structure can overcome the reunion of two-dimentional carbon material such as graphene to show
As there is more preferable electrochemical energy storage characteristic, have in secondary cell such as lithium ion battery and sodium ion battery electrode material wide
Application prospect.Therefore, development technology is simple, quick, cost is low and pollutes small network-like carbon negative pole material controllable preparation is
The key for making it be able to promote development in the application of each field.
The content of the invention
It is an object of the invention to provide a kind of low cost, technique is simple and is easy to the network-like carbon negative pole material of batch preparation
Method.
The present invention is used as electrolyte using alcoholic solvent and alkali, and network-like carbon negative pole material is obtained by post processings such as electrolysis,
Advantage protrudes in terms of scale magnanimity preparation.
A kind of preparation method of network-like carbon negative pole material, it is characterised in that this method comprises the following steps：
1）Sodium hydroxide or potassium hydroxide are dissolved in methanol, ethanol or isopropanol, forerunner's reactant is obtained through electrolysis；
2）By step 1）Products therefrom is rotated, is freeze-dried, in inert nitrogen gas, argon gas or reducibility gas nitrogen atmosphere
Under enclosing, network-like carbon negative pole material is obtained after annealing 30-180min, cleaned again and drying at 500-800 DEG C；
3）In step 1）In electrolyte by adding sulfur-bearing or nitrogen-containing compound electrolysis after, then through step 2）Processing obtains network-like
Carbon negative pole material.
Sulfur-bearing or nitrogen-containing compound of the present invention are thiocarbamide, thioacetamide, urea or DMF.
Network-like carbon negative pole material has open, porous, interworking architecture, overcomes flaky material agglomeration, lithium from
Son and sodium-ion battery equal energy source field of storage have a good application prospect.
The invention has the advantages that：
1）Material therefor is cheap, nontoxic, and cost is low.
2）Easy to operate controllable, easily doping is reproducible.
The effect benefit of the present invention：A kind of method that simple scale prepares carbon negative pole material is provided, raw materials are rich
Rich, cheap and easy to get, environment-friendly, reproducible, stable and reliable product quality.
Brief description of the drawings
Fig. 1 is the network-like carbon negative pole material lithium ion half-cell multiplying power property figure of gained in embodiment 1.
Fig. 2 is the network-like carbon negative pole material sodium ion half-cell cycle characteristics figure of gained in embodiment 1.
Fig. 3 is the TEM photos of the network-like carbon negative pole material of gained in embodiment 1.
Fig. 4 is the SEM figures of the network-like carbon negative pole material of gained in embodiment 2.
Fig. 5 is the network-like carbon negative pole material lithium ion half-cell cycle characteristics figure of gained in embodiment 3.
Embodiment
Embodiment 1
Sodium hydrate solid 2g will be added in 200ml alcohol solvents, be stirred well to and be completely dissolved.Using platinum electrode and Titanium
Piece applies 80V voltages, is electrolysed 200min, can obtain dark brown precursor liquid as electrode.Presoma is rotated, with steaming
It is freeze-dried after distilled water is scattered.By cold dry rear powder under the protection of inert atmosphere argon gas, 600 DEG C are annealed 1 hour, and natural cooling obtains
To solid powder.After powder is cleaned with watery hydrochloric acid and distilled water, 60 DEG C of drying, network-like carbon negative pole material is obtained.Gained net
Network shape carbon has good multiplying power property as lithium ion battery and anode material of lithium-ion battery（Fig. 1）And cycle characteristics（Figure
2）.Network-like carbon negative pole material obtained by the embodiment of the present invention has obvious open network interconnection pattern.Fig. 3 is implementation of the present invention
The TEM photos of the middle network-like carbon negative pole material of gained, it can also be seen that prepared carbon material has obvious network through knot
Structure.
Embodiment 2
Sodium hydrate solid 0.8g will be added in 200ml alcohol solvents, be stirred well to and be completely dissolved.Using platinum electrode and metal
Titanium sheet applies 100V voltages, is electrolysed 120min, can obtain dark brown precursor liquid as electrolysis electrode.Presoma is revolved
Steam, be freeze-dried after being disperseed with distilled water.By cold dry rear powder under reducing atmosphere hydrogen/argon gas, 600 DEG C are annealed 1 hour, from
So cooling obtains solid powder.After powder is cleaned with watery hydrochloric acid and distilled water, 60 DEG C of drying, network-like Carbon anode material is obtained
Material.Fig. 4 is the SEM photograph of network-like carbon negative pole material obtained by the embodiment of the present invention, has obvious open network interconnection pattern.
Embodiment 3
Sodium hydrate solid 1.2g and thioacetamide 0.8g will be added in 250ml alcohol solvents, be stirred well to and be completely dissolved.
Using platinum electrode and metal titanium sheet as electrolysis electrode, apply 100V voltages, be electrolysed 120min, can obtain dark brown precursor liquid
Body.Presoma is rotated, is freeze-dried after being disperseed with distilled water.By cold dry rear powder under the protection of inert atmosphere argon gas,
700 DEG C are annealed 1 hour, and natural cooling obtains solid powder.After powder is cleaned with watery hydrochloric acid and distilled water, it is small to dry 24 at 60 DEG C
When, obtain sulfur doping carbon negative pole material.Fig. 5 is circulation of the gained carbon material as lithium cell cathode material in the embodiment of the present invention
Performance, 1 peace/gram current density under, specific capacity be higher than 500 MAhs/g.
Embodiment 4
Potassium hydroxide solid 1g will be added in 200ml methanol solvates, be stirred well to and be completely dissolved.Using platinum electrode and Titanium
Piece applies 150V voltages, is electrolysed 40min, can obtain dark brown precursor liquid as electrolysis electrode.Presoma is rotated,
It is freeze-dried after being disperseed with distilled water.By cold dry rear powder sample under the protection of inert atmosphere argon gas, 550 DEG C are annealed 1 hour, from
So cooling obtains solid powder.After powder is cleaned with watery hydrochloric acid and distilled water, 60 DEG C of drying, network-like Carbon anode material is obtained
Material.
Embodiment 5
Sodium hydrate solid 0.5g will be added in 100ml isopropanol solvents, be stirred well to and be completely dissolved.Using platinum electrode and gold
Belong to titanium sheet as electrolysis electrode, apply 200V voltages, be electrolysed 30min, obtain precursor liquid.Presoma is rotated, with steaming
It is freeze-dried after distilled water is scattered.By cold dry rear powder sample under the protection of inert atmosphere argon gas, 650 DEG C are annealed 1 hour, naturally cold
But solid powder is obtained.After powder is cleaned with watery hydrochloric acid and distilled water, 60 DEG C of drying, network-like carbon negative pole material is obtained.
Embodiment 6
Sodium hydrate solid 0.5g and urea 0.3g will be added in 100ml isopropanol solvents, be stirred well to and be completely dissolved.Using
Platinum electrode and metal titanium sheet apply 100V voltages, are electrolysed 100min, can obtain precursor liquid as electrolysis electrode.By presoma
Rotated, and be freeze-dried after being disperseed with distilled water.By cold dry rear powder sample under the protection of inert atmosphere argon gas, 750 DEG C
Annealing 1 hour, natural cooling obtains solid powder.After powder is cleaned with watery hydrochloric acid and distilled water, 60 DEG C of drying, obtain nitrogen and mix
Miscellaneous network-like carbon negative pole material.Understand that nitrogen element content is in 3at% through energy spectrum analysis.
Embodiment 7
Sodium hydrate solid 0.8g and DMF 5ml will be added in 100ml isopropanol solvents, be stirred well to
Fully dissolved.Using platinum electrode and metal titanium sheet as electrolysis electrode, apply 250V potential electrolysis 40min, obtain precursor liquid.Will
Presoma is rotated, and is freeze-dried after being disperseed with distilled water.By cold dry rear powder sample under the protection of inert atmosphere nitrogen,
700 DEG C are annealed 1 hour, and natural cooling obtains solid powder.After powder is cleaned with watery hydrochloric acid and distilled water, 60 DEG C of drying, obtain
To the network-like carbon negative pole material of N doping.
Embodiment 8
Potassium hydroxide solid 0.8g and thioacetamide 0.3g will be added in 200ml methanol solvates, be stirred well to and be completely dissolved.
Using platinum electrode and metal titanium sheet as electrolysis electrode, apply 100V voltages, be electrolysed 80min, can obtain precursor liquid.By forerunner
Body is rotated, and is freeze-dried after being disperseed with distilled water.By cold dry rear powder sample under the protection of inert atmosphere argon gas, 750
DEG C annealing 2 hours, natural cooling obtains solid powder.After powder is cleaned with watery hydrochloric acid and distilled water, 80 DEG C of drying, sulphur is obtained
Adulterate network-like carbon negative pole material.
Embodiment 9
Potassium hydroxide solid 0.8g and thiocarbamide 0.3g will be added in 200ml alcohol solvents, be stirred well to and be completely dissolved.Using platinum
Electrode and metal titanium sheet apply 100V voltages, are electrolysed 80min, can obtain precursor liquid as electrolysis electrode.Presoma is carried out
Revolving, and be freeze-dried after being disperseed with distilled water.By cold dry rear powder sample under the protection of inert atmosphere argon gas, 750 DEG C of annealing 2
Hour, natural cooling obtains solid powder.After powder is cleaned with watery hydrochloric acid and distilled water, 80 DEG C of drying, sulfur doping net is obtained
Network shape carbon negative pole material.
Claims (2)
1. a kind of preparation method of network-like carbon negative pole material, it is characterised in that this method comprises the following steps：
1）Sodium hydroxide or potassium hydroxide are dissolved in methanol, ethanol or isopropanol, forerunner's reactant is obtained through electrolysis；
2）By step 1）Products therefrom is rotated, is freeze-dried, in inert nitrogen gas, argon gas or reducibility gas nitrogen atmosphere
Under enclosing, network-like carbon negative pole material is obtained after annealing 30-180min, cleaned again and drying at 500-800 DEG C；
3）In step 1）In electrolyte by adding sulfur-bearing or nitrogen-containing compound electrolysis after, then through step 2）Processing obtains network-like
Carbon negative pole material.
2. the method as described in claim 1, it is characterised in that sulfur-bearing or nitrogen-containing compound are thiocarbamide, thioacetamide, urea
Or DMF.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105810914A (en) * | 2016-05-13 | 2016-07-27 | 中南大学 | Sulfur-doping porous carbon material of sodium ion battery and preparation method of sulfur-doping porous carbon material |
| CN106006599A (en) * | 2016-05-11 | 2016-10-12 | 浙江工业大学 | Synthesizing method and application of high-S-content P-S-N-codoped mesoporous carbon material |
| CN106115653A (en) * | 2016-06-22 | 2016-11-16 | 兰州理工大学 | A kind of preparation method of the porous carbon materials of Heteroatom doping |
| CN106504906A (en) * | 2016-12-01 | 2017-03-15 | 中国石油大学(华东) | Carbon quantum dot/nickel hydroxide electrochemical energy storage materials, synthetic method and application |
-
2017
- 2017-07-01 CN CN201710529304.0A patent/CN107369833A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006599A (en) * | 2016-05-11 | 2016-10-12 | 浙江工业大学 | Synthesizing method and application of high-S-content P-S-N-codoped mesoporous carbon material |
| CN105810914A (en) * | 2016-05-13 | 2016-07-27 | 中南大学 | Sulfur-doping porous carbon material of sodium ion battery and preparation method of sulfur-doping porous carbon material |
| CN106115653A (en) * | 2016-06-22 | 2016-11-16 | 兰州理工大学 | A kind of preparation method of the porous carbon materials of Heteroatom doping |
| CN106504906A (en) * | 2016-12-01 | 2017-03-15 | 中国石油大学(华东) | Carbon quantum dot/nickel hydroxide electrochemical energy storage materials, synthetic method and application |
Non-Patent Citations (2)
| Title |
|---|
| HONGSHUAI HOU等: ""Carbon Quantum Dots and Their Derivative 3D Porous Carbon Frameworks for Sodium-Ion Batteries with Ultralong Cycle Life"", 《ADVANCED MATERIALS》 * |
| S.KUNDOO等: ""Electron field emission from nitrogen and sulfur-doped diamond-like carbon films deposited by simple electrochemical route"", 《MATERIALS LETTERS》 * |
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Application publication date: 20171121 |